Adsorption-fractionation process



March 31, 1953 L. D. ETHERINGTON 2,533,207'

V ADSORPTION-FRACTIONATION PROCESS I' Filed April 1s, 1949 Lewis Etherrzgon Graver-:Lor

Patented Mar. 31, 1953 y ADSORPTION-FRACTIONATION PROCESS Lewis D. Etherington, Bayonne, N. J., assigner to Standard Oil Development Company, a. corporation of Delaware Application April 13, 1949, Serial No. 87,260 12 Claims. (Cl. 18S-114.2)

This invention relates to an improved continuous adsorption process employing solid adsorbents for the fractionation of components of Va gaseous mixture in an adsorption tower by countercurrent contact with the gaseous mixture and the solid adsorbent. Specifically, the invenftion is concerned with the stagewise addition of --heat in the adsorption-desorption process, and

particularly with the addition of heatv to the rectifying section of the adsorption tower.

The fractionation of a'gaseous mixture by 1 causing it to flow upwardly through an adsorption zone where it contacts an adsorbent materrialy such as charcoal, silica gel, etc., in small particle or powdered form which is passed downwardly through this zone and through a rectifying zone belowv the point of feed gas entry has already been described. The adsorbent leaving the bottom of the rectifying zone is heated, with or without contact with a stripping ygas such as `steam, to desorb the adsorbed component of `the gas which is separately recovered. The hot stripped adsorbent is then dehydrated, if desired or necessary, cooled, and returned to the T top of the adsorption zone for re-use.

In previously described continuous processes for the adsorptive separation of gases, feed gas constituents are adsorbed and rectified into various fractions in a countercurrent tower operation.

- The reflux vapor, which is returned to the bottom of .the lower rectication zone, plus the cycle. The adsorption and rectifying tower sections operate adiabatically except for a small heat loss to the surroundings.

4It is an object of this invention to provide a continuous countercurrent adsorption-desorption process featuring reduced heat transfer surface requirements in the desorption phase of the process. y

It is also an object of this invention to provide a continuous countercurrent adsorptiondesorption process which permits the use of heating media ofl reduced average temperature.

. It is an objectof the present invention to employ desorbed rhot adsorbent for heating the adsorbent in the rectification section ofthe adsorptionzona It is a further object of this invention to reduce theexce ssive adsorber vapor volumes between l the desorber heating section vand the bottoms -product drawoif point as encountered infpreviously` described continuous adsorptionprocesses. W Y --f These and other objects of this invention are accomplished by effecting the desorption in two or more heating zones instead of the single primary heating zone employed inthe customary desorption operation. Itisa feature-of this invention to add heat to the adsorption zone particularly inthe rectifying section,- and more particular-ly in the lower area of-the rectifyingsection. f

Data obtained on charcoal 4circulation fand tower stage requirements for the adsorptive separation of C2 and C3 hydrocarbon fractions from methane andA less readily adsorbed gases contained in petroleum refinery gas indicate that the de-ethanizer rectifying section of the adsorption zone may be operated at a higher temperature level without additional required charcoal circulation provided a few additional rectifying stages are used.

In one phase of the present invention itis proposed to heat the adsorbent in at least two ,zones instead of one in order to realize a decrease in heating surface requirements, to eiect more complete heat exchange between hot and cold adsorbent streams which results in reduced extraneous heating and cooling require- Vments and cooling surface, to permity the use of a lower average temperature heating medium in the desorber, and to reduce excessive vapor volumes in the desorber. y

Suitable apparatus for use in the processrof this invention is shown,diagrammaticallyin the attached drawing. The figure represents-a section elevational view of one'type of apparatus adapted to carrying out the process of the invention.

Referring to the drawing the invention will Vbe described for purposes of example only'by 8, a 03+ vapor removal line 9, a secondaryheating zone I 0 containing heating unit 26 located in the de-ethanizing section, a desorber section I I, a steam entry line I2 and a solids withdrawal line I3. The desorber section I I contains the primary heating zone 28 equipped with one or more heating coils 21.

The feed gas comprising a mixture of methane, C2 hydrocarbons, C3 hydrocarbons and less readily adsorbed components such as nitrogen and hydrogen is introduced, usually under pressure, into the adsorption tower via line 4 at a point between the adsorption section and the rectication section. A mass of charcoal .adsorbent cooled to approximately 120 F.-200 F. is introduced into the top of the adsorption Vsection of the tower at the disengaging sectionvia'line'll. The adsorption tower may be operated as a soaker type reactor in which the tower .is `packed with solid adsorbent which gravitates slowly from the top to the bottom of the tower, or the tower may be operated with uidized charcoal in "which event the tower will contain trays lfspaced 4at regular intervals and -upon which the 'charlcoal Will build up -andreach a level indicated by the numeral I6. The adsorbent passes down the v'tower Aat 'such `a rate that substantially all the C2 and heavier hydrocarbons are selectively adsorbed on the ladsorbent within the adsorption lsection while the methane and lighter components,e. g., nitrogen and hydrogen,'pass overhead Yvia cyclone Il and leave vthe tower via line I8. "Entrained charcoal'separated from this gas irials flow upwardly past the gas 'feed line `ll into 'the adsorber section and are eventually withdrawnfrom the system via line I8.

In the lower area of therectiication section, ige., in the de-ethanizing section 1, the adsorbent is refluxed'with the heavier components of the vhydrocarbon Ifeed, for example, the Ca-I- hydrocarbons similarly released 'in the lower section of the tower bythe action of the-desorber I I and the secondary heating zone l0, whereby the desorpition of the Czhydrocarbons is brought about. 'The 'C2 hydrocarbons containing controlled amounts of methane and unavoidable small equilibrium quantities of Cs-lvhydrocarbons are removed in controlled amounts as `a vapor stream from a point near the center of the rectification section Avia line 8 at a temperature of about 20W-240 F.

The charcoal substantially free of C2 and lightler -components passes from the lowermost area `of the rectication section into the desorlber II containing the primary heating zone 28. In 'the desorber the desorption of the Cs-I- hydrocarbons is accomplished by means of stripping vapor such as steam and by heat supplied indirectly to the enriched char-coal by suitable heating means such as by condensation of high boiling liquid such as diphenyl or a, mixture of -diphenyl and diphenyl oxide, by hot 'flue gas,

etc. The action ofthe heat together with the countercurrent stripping action of steam introduced via-line I2 disengages the Ca-lhydrocarbons from the adsorbent. These hydrocarbons pass upwardly through the desorber section. The product portion is Withdrawn through line 9 at a temperature of about 350 F. and the remaining portion is returned as reux vapor tothe bottom of the rectication section 5. The C3-}- stream contains appreciable amounts of water vapor which may be removed therefrom by appropriate cooling or quenching operation.

The 03+ reflux Vapor from the desorber also contains an appreciable quantity of steam. This reflux may also be quenched or cooled for steam removal before passing to the recticaticn section, or may be passed to this section as wet gas. En thellatter case, the major portion of the refluxed'steam is *adsorbed in the rectication section andreturns to the desorber, i. e., there is an internal recycle of steam between the two tower sections. When the reflux vapor is dried before introduction into the rectication section as described, the addition of heat to the rectiiica- `tion section reduces the excessive amount of reiiux C-I- vapor to v`be quenched .or cooled and there is an attendant reduction in Yrequired cooling, heating and heat exchangesurface for the overall adsorption process.

Additional sidestreams representing one or more intermediate cuts may be obtained by expanding the rectifier section and removing, in addition to a more vconcentrated C3 product, heavier hydrocarbons such as C4 and C5 streams at lower points in the rectier section. The major component vof each additional sidestream would be contaminated chieiiy with small lequilibrium quantities of heavier material.

The hot stripped charcoal from the desorber section Il at a temperature Yof about 500 F. is

Yremoved via line I3 vand circulated via gas lift line I4 with the assistance of tail gas to a cooling Zone 20 in which the charcoal is cooledto a temperature in the range of F. to 200 F. The cooled charcoal enters the top Vof the disengaging section 2 via line I. In the disengagingsection the recycled tail gas employed as Ylift gas plus the net tail gasoverhead from the adsorption zone are removed via line I8 while the charcoal descends into the tower to repeat the cycle.

Although the secondary heating zone I0 has been illustrated by a single heating unit consisting of a single stage, this single unit may comprise two or vmore adjacent stages; or, two .or more units separated by adiabatic portions of the de-ethanizing section 'I may be lemployed with eachunit consisting of Aone or more adjacent stages. The adsorbent and contacting vapor wil1 beat progressively'increasing average temperature levels in the various stages, moving downwardly in the tower, such that the benefits described in the following paragraph will be at a maximum. It is usually preferable to locate the units of the secondary heating zone I0 in the de-ethanizing section below the immediate vicinity of the point of withdrawal of the intermediate C2 product vapor sidestream in order to minimize the unavoidable equilibrium quantities of Ca-ihydrocarbonsin the C2 product.

Although the primary heating zone 28 contained in the desorber I I has been illustrated as a single stage, two or more adjacent stages at progressively increasing temperatures (moving downwardly) may be used, resulting in decreased required primary heating surface for a given constant temperature heating media used throughout the primary heating zone. The use of more 'than one primary heating stage is particularly "advantageous when using iiuidized adsorbent.

From the above description it will be apparent that a portion of the total heatingV load required forcdesorptionf f the charcoal is added in the secondaryheating zone Il] in the de-ethanizing (C3-enriching) adsorber section above the desorber andthe remaining heat is added at the bottomV of the tower in the primary heating zone 28 contained in the desorber II. In supplying al portion of the total heat to the lower portion of the rectifying zone instead of all the heat 'tothe desorber the average temperature level of -thecharcoal being heated is lowered and the total Vheat transfer surface requirements are reduced v4'when `using heating media at the same high temperature .forl :both heating..V zones. Alternately, the`A` average temperature levelfof the heating media for the secondary heating zone IU may be lowered thereby permitting the use of less expensive extraneous heatingmedia. As a further alternative, the hot stripped charcoal from the `bottom of thedesorber may be used as the heatingllwmedium for heating the rectifying section,

:.i. e., by indirect heat exclrange between'the hot desorber exit charcoal and the colder charcoal in theadsorber rectifying section. Thus, in effec- -tively utilizing the sensible heat of the hot delsorbed charcoal, the amount of required extraneous heaty addition is reduced, the amount of Vrequired coolant suchV as cooling water to cool the hot desorbed adsorbent for its re-use in the adsorption section is reduced, and the required cooling surface is reduced.

When using more than one stage in the primary Aheating zone contained in the desor-ber as previ- .,ouslydescribed such that the upper stages of this .zoneare operated colder than the lower stages ,Qf. the said heating zone, hot desorbed charcoal `from the bottom of the desorber may also be heat exchanged against the colder charcoal in the upper`heat ing .stages of thedesorber to obtain recovery of sensible heat fromrthehot desorbed charcoal. However, heat exchange of the hot c lesorbed char-coal with charcoal in the rectication section provides for more'complete recovery ofk hot-charcoal sensible heat and with less required heat exchange surface due toI the lower temperature of the charcoal in the re-ctifyingv -sectionas compared to temperatures of charcoal in the top desorber heating stages.

Usually, no more than three primary heating zone stagesoperating simultaneously as stripping stages-.in the desorberII, are justied when using afluidized adsorbent. However, additional 'adiabatic'lon non-heated stripping stages are usually desired for the desorber in`- order to minimize the required stripping steam. When using more than one primary heating zone stage, it is usually desirable that these stages be ad- 'jacent rather than be separated by non-heated desorber stages. The primary heating zone may `comprise one or more of the top desorber stages, or the -heated desorber stages may be located ,between non-heated adsorber stages as illustratedr Also, heating by means of the primary heating zone may -be yeffected throughout the `desorber section. i

"11n the customary operation the desorber heating` medium is maintained at a temperature in rvthe vicinity of 600 F.7 00 F. in the heating tubes which requires the use of expensive, high temperature condensation materials asl previously rmentioned, gas red heaters, or high pressure steam which is outside the-.range of that normal- 'ly available'inthe-refinery." By the use of vstage heating as described in this invention itis possible to lower the average temperature oi` the heating medium in al1 orpart of the heating system; f Y

circulation than the adsorption and rectification `of the C3 fraction. Therefore,when both C2 and Caffractions are being adsorbed and separated simultaneously in a single adsorber,there is considerably more charcoal lcirculation through the de-ethanizer adsorber section 1 perunit-a'mo'unt of C3 product than-would be practical when adsorbing only `C3 from' 1a 'feed gas containing 'C1 through `Ci hydrocarbons; Thus, for the former separation case,r the amounts yof adsorbed' and vapor reflux phases in the de-ethanizing: section 'are necessarily excessive when no heat isfadded to this section, and the required number of stages for the de-ethanizing adsorber section is vvery small. The existence of this condition has been found to tolerate thev addition of heat to the deethanizing section 1 which reduces the adsorbed and reux vapor phases in this section without an appreciable increase in the required number of rectifying stages and'with no required increase in the charcoal circulation. The addition of heat to the rectifying section takes a considerable heat load off the desorber heating zone so that the advantages previously described may be realized. Also, inA reducing the excessive amount of reflux vapor (by the `addition of heat to the rectification zone), which, together with the C3 product and the stripping steam, constitutes the tower vapor load betweenfthetop primary heating zone stage and the C3 product withdrawal line, the diameter of this section of the adsorber, normally excessive, may be reduced appreciably.

These advantages of the present invention may be realized also in the adsorptive separation of a feed gas into only two separate fractions with a single tower but to an indicated lower extent than when separating the feed mixture into three or more fractions in a single tower operation.

Due to the comparatively low temperature of the de-ethanizer section 'I, low-temperature heat may be applied to the secondary heating zone I0 by high pressure steam, by low temperature diphenyl or diphenyl-diphenyl oxide mixtures, or by the desorbed hot charcoal circulated from the bottom of the desorber via lines I3 and 2| through the heater 26 in solids-to-solids heat exchange. To accomplish the latter, all or a portioniof the hot charcoal is withdrawn from line I3 via line 2|, and, with the assistance'of lift gas in line 22 withdrawn from line I4, is carried through the coils of heater 26. From the heater 26 the charcoal, which has given up some of its sensible heat, is introduced into cooler 20 via lines 23 and I4 for additional cooling. The hot desorbed charcoal inside the coils of heater I0 may exist as a dense fluidized solid, similar to the colder solid in the de-ethanizing section, in 'order .to obtain maximum overall heat transfer coeilicients when heat exchanging the two solid streams.

Although the addition of heat to the rectify- `ing section has been described by means of an byothersuitable means. Forexample, charcoal .may be removed from the rectifying section, yheated in an -external :heater aand returned to Lthe rectifying section at the desired point. -Similarly a vapor stream may be removed from the .rectifying section,. heated externally and returned `to lthe 'towerin contact with the -charcoal in the rectifying section. However,.it is preferable to Aadd heat to the rectifying section `by means of heating the adsorbent therein rather than by heating the vapor.

The multi-stage heating described in the adscrption process of this invention is independent of the mannerin which the charcoal is cooled. The Acharcoal .may be totally cooled vin the one coolingzone located `inside of ior `outside of the .iadsorption tower, or the cooling may be done stage-wise -in two or more cooling zones all located outside .the adsorption '.tower, kall located within the adsorption tower, or some cooling zones may beA located outside the adsorption tower while others .are located within the adsorption tower. The manner in which the charcoal is cooled is not a subject of this invention.

In the process illustrated in the drawing the tail gas emerges from the adsorption tower Via line :I8 and is removed in part via line 24 as -netproduct to a'tail gas water scrubber or lter (not illustrated) where the remaining entrained charcoal of ne particle size is removed therefrom. A portion of the tail gas is removed via -line 25, repressured by blower I9 and recycled as liftvgas via line I4 to carry the desorbed hot charcoal through the cooling zone and back into ythe adsorption tower.

It is understood that during the adsorption- `desorption cycle some of the charcoal adsorbent will become deactivated thus requiring regeneration. The `regeneration is carried out by conventionalmeans and isnot a part of this inven- `tion.

Itis preferred to remove acidic gases such as carbon dioxide and hydrogen sulfide from the hydrocarbon feed to the charcoal adsorbent fractionationprocess by suitable pretreatment of the feed before it enters the adsorption zonein order to minimize metal corrosion and contamination of products.

When the system is operated employing a fiuidized asorbent in the adsorption tower the adsorbent is handled as a dense fluid bed in which the particles average approximately 50-20@ micron particle size. The particles possess considerable vmotion reative'to each other Vand plates or packing are required Vin the tower in order to effect suiiicient countercurrentcontact between the ad- "sorbent and vapor. The tower maybe supplied with perforated -plates equipped with simple standpipe overflows, the vapor passing upwardly through the plate perforations at a velocity sufl'ciently high to prevent downward passage of lcharcoal therethrough and to provide good solids lfluidization. Packing or bubble-cap piates can valso be employed. Approximately l to 3 feet of dense bed and 2 feet of vapor disengaging space iper plate are adequate to establish a satisfactory approach to equilibrium between vapor and solid within'a single stage when using fiuidized adsorbent. In the moving-bed type of operation the feed gas is fed to the tower at a point near the center thereof. The tower is packed with an adsorbent of approximately 10 to 30 mesh in size `which in the case of charcoal would amount to -a bulk density of about 30 lbs. per cubicft, The '.tower .is usually :operated under approximately f8 the same pressure at Jwhich the feed gas is available. The packed adsorbent gravitates at a predetermined rate from the top to the bottom of the tower as previously described.

The charcoal inventory in a tower of a given diameter and height is much smaller when the adsorbent is fluidized than when it is handled as a moving-bed, and fluidized solids permit much higher allowable tower vapor velocities. Also, much higher heat transfer coeflicients are obtained with uidized solids than with close packed solids.

The invention is generally applicable to fractionation processes of the type illustrated above, involving selective adsorption of one or more components from a mixture containing other components which are more or less readily adsorbed. In such operations it may be used to separate hydrocarbon mixtures into fractions of different boiling range or chemical structure by suitable selection of adsorbents and stripping agents in conformity with chromatographic principles. For example, paraiiins, naphthenes, olefins, diolens and aromatics may be obtained as separate fractions from mixtures of two or more of these classes of hydrocarbons with a silica gel adsorbent used in an adsorption process as described above in one or more stages according to the number of fractions to be separated. Similarly, organic vapors of different degrees of polarity may also be separated by selective adsorption onany suitable solid adsorbents.

The process is particularly applicable to the recovery of C2 and C3 hydrocarbons from refinery fuel gas; to the recovery of light ends from lowpressure catalytic cracking gases; to the recovery of hydrocarbons and oxygenated compounds from hydrocarbon synthesis gas produced at low pressures; to the separation of methane from nitrogen; to the recovery of acetylene from the gases of the Wulff process, and to the separation of C2, hydrogen sulfide, and light oil fractions from coke-oven gas.

What is claimed is:

1. A continuous process for the separation of gaseous components of a mixture comprising a less readily adsorbed component A, a more readily adsorbed component C, and an intermediate component B by means of adsorption by a solid absorbent which comprises, passing said adsorbent downwardly through an adsorption zone having an adsorption section above the gaseous mixture feed-point, a middle rectification section and a lower desorption section below the gaseous mixture feed-point, continuously feeding the gaseous mixture to a lowerportion of the adsorption section, removing unadsorbed component A from an upper portion of the adsorption zone, passing the adsorbent containing adsorbed thereon components B and C into said rectification section, removing component B from a point near the center of the rectification section, heating the adsorbent in the lower portion of said rectification section to an extent sufiicient to cause vaporization of a substantial proportion of component C from the downflowing adsorbent therein, passing the adsorbent containing remaining undesorbed component C adsorbed thereon into the desorption section, and recovering remaining undesorbed component C by heating and stripping the adsorbent in the desorption section.

2. A process according to claim 1 in which steam is added to the desorption zone to assist in the desorption of component C.

3. A process according to claim 1 in which heat is supplied to the lower section of the rectification section by passing therethrough in indirect heat exchange hot solid adsorbent recovered from the desorption section. u

4. A continuous process for concentrating a C2 hydrocarbon fraction from a gaseous mixture comprising methane, C2 hydrocarbons and Ca hydrocarbons by means of adsorption by a solid adsorbent which comprises, passing said adsorbent downwardly through an adsorption zone having an adsorption section above rthe gaseous mixture feed-point, a middle rectification section and a lower desorption section below; the gaseous mixture feed-point, continuously feeding the gaseous mixture to a lower portion of the adsorption section, removing unadsorbed methane from the upper portion of the adsorptionjzone, passing the adsorbent containing adsorbed thereon substantially Cz and C3 hydrocarbons into the rectification section, heating the adsorbent in the lower -portion of said rectification section to an extent suicient to cause vaporization of a substantial portion of C3 hydrocarbons from the downiiowing adsorbent, removing C2 hydrocarbons from a point near the center of the rectification section, passing the adsorbent containing remaining undesorbed substantially C3 hydrocarbons adsorbed thereon into the desorption section, and recovering remaining undesorbed C3 hydrocarbons vby heating and stripping the adsorbent in the desorption section.

5. A process according to claim 4 in which hot adsorbent is removed from the desorption section and passed through the lower section oi the rectiiication Zone in indirect heat exchange.

6. A process according to claim 4 in which the adsorbent is charcoal.

'7. A process according to claim 4 in which the gaseous mixture also contains C4 hydrocarbons which are removed from the adsorbent with the Cs hydrocarbons.

8. A process according to claim 4 in which gaseous mixture also contains less readily adsorbable components which pass overhead from the adsorber with the methane.

9. A process according to claim 4 in which the gaseous mixture comprises methane, ethane, ethylene, propane and propylene.

10. A process according to claim 4 in which the solid adsorbent is fiuidized carbon.

11. A process according to claim 4 in which the adsorbent is in a iiuidized condition throughout the process and in which a portion of C3 hydrocarbons vaporized in the desorption section is removed as net product and the remaining portion is reuxed to a bottoms portion of the rectication section to fluidize the adsorbent therein.

12. A process according to claim 4 in which heat is supplied to the adsorbent in the lower portion of said rectification section by indirect heat exchange.

LEWIS D. ETHERINGTON.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date 1,422,007 Soddy July 4, 1922 2,250,716 Legatski July 29, 1941 2,348,009 Johnson et al May 2, 1944 2,412,025 Zimmerman Dec. 3, 1946 2,495,842 Gilliland Jan. 31, 1950 2,522,059 Ray et al. Sept. 12, 1950 2,529,289 Gilliland Nov. 7, 1950 FOREIGN PATENTS Number Country Date 317,629 Great Britain Aug. 22, 1929 OTHER REFERENCES Hypersorption Process for Separation of Light Gases," Clyde Berg, Transactions of A. I. Ch. E., vol. 42, No. 4, 1946, pages 665-680. 

1. A CONTINUOUS PROCESS FOR THE SEPERATION OF GASEOUS COMPONENTS OF A MIXTURE COMPRISING A LESS READILY ADSORBED COMPONENT A, A MORE READIILY ADSORBED COMPONENT C, AND AN INTERMEDIATE COMPONENT B BY MEANS OF ADSORPTION BY A SOLID ABSORBENT WHICH COMPRISES, PASSING SAID ADSORBENT DOWNWARDLY THROUGH AN ADSORPTION ZONE HAVING AN ADSORPTION SECTION ABOVE THE GASEOUS MIXTURE FEED-POINT, A MIDDLE RECTIFICATION SECTION AND A LOWER DESORPTION SECTION BELOW THE GASEOUS MIX TURE FEED-POINT, CONTINOUSLY FEEDING THE GASEOUS MIXTURE TO A LOWER PORTION OF THE ADSORPTION SECTION, REMOVING UNADSORBED COMPONENT A FROM AN UPPER PORTION OF THE ADSORPTION ZONE, PASSING THE ADSORBENT CONTAINING ADSORBED THEREON COMPONENTS B AND C INTO SAID RECTIFICATION SECTION, REMOVING COMPONENT B FROM A POINT NEAR THE CENTER OF THE RECTIFICATION SECTION, HEATING THE ADSORBENT IN THE LOWER PORTION OF SAID RECTIFICATION SECTION 